205047 Λ6 B6 經濟部中央標準局貝工消費合作社印製 五、發明説明（） 本發明是有關在氣相中製備乙烯聚合物或乙烯與至少 一含3至12値磺原子之α-烯烴之共聚物的方法。此方法 使用一値高活性觸媒条統。 戚格勒-納他型觸媒条統包括一含有至少一個轉移金 屬（例如鈦）化合物之觸媒，和一含有至少一傾有機金饜 化合物（其金颶如鋁）的共觭媒。眾所皆知，當觭媒包含 轉移金屬化合物被使用為含有固體無機化合物（例如氛化 鎂）之支持體，則對於這些觸媒的性質有很大影響。製備 觸媒支持體的技術，其支持體的性質和製備觸媒的方法通 常包括固定轉移金屬化合物於支持髏上，此對於觸媒的性 質是非常重要。 從法國専利FR-B- 2 , 5 29 , 2 1 1知道：於氣相中，在流 化床反應器中聚合烯烴之方法包括預先聚合步驟。此 方法所使用之觸媒糸統包括：（1)含有鈦化合物附在固態 氣化鎂支持體上之觸媒，和（2)含一有機鋁化合物之輔觸 媒。然而，在FR-B- 25 292 1 1所使用之觸媒含低量之鈦成分 ，對石蠟聚合反應，特別是對乙烯的聚合或共聚合反應具 普通之活性。事實上，製備得之聚合物或共聚物的産率很 低，且殘餘高量之鈦成分。當所使用之觸媒含徹量鈦則聚 合物或共聚物殘餘的氣成分較高*當在氣相中以此方法製 備某些共聚物，則共聚物形成較具黏性之粒子，這些粒子 凝集成團。特別在流化床反應器中，使用此種觴媒，製備 非常低密度之線型聚乙烯類，很難不形成大量凝集團。此 現象會终止此聚合反應。 (請先閲讀背面之注意事項再填寫本頁) 裝· 線· 木紙張尺度遑用中SB家標準(CNS)甲4規格(210><297公*) - 4 - Λ6 B6 20504? 五、發明説明（） (請先閱讀背面之注意事項再填寫本頁) 在氣相中製備乙烯聚合物或共聚物的新方法已被發現 。此方法使用具高活性之觸媒糸統。使用此觸媒糸统可克 服或減輕上述己知方法之問題。特別是它可製備高産率且 含非常少量觸媒殘餘物之乙烯聚合物或共聚物。而且，此 方法可在氣相中製備較高黏性之乙烯共聚物和非常低密度 之線型聚乙烯而不會形成凝集圃。205047 Λ6 B6 Printed by Beigong Consumer Cooperative of Central Bureau of Standards of the Ministry of Economy V. Description of the invention () The present invention relates to the preparation of ethylene polymer in the gas phase or the copolymerization of ethylene with at least one alpha-olefin containing 3 to 12 sulfon atoms Methods. This method uses a high activity catalyst system. The Ziegler-Natta catalyst system includes a catalyst containing at least one transfer metal (such as titanium) compound, and a common catalyst containing at least one organic metal compound (the gold of which is like aluminum). It is well known that when a media containing a transfer metal compound is used as a support containing a solid inorganic compound (for example, magnesium oxide), the properties of these catalysts are greatly affected. The technology of preparing the catalyst support, the nature of the support and the method of preparing the catalyst usually include fixing and transferring the metal compound on the supporting skeleton, which is very important for the properties of the catalyst. It is known from the French FR-B-2, 529, 211: In the gas phase, the method of polymerizing olefins in a fluidized bed reactor includes a pre-polymerization step. The catalyst system used in this method includes: (1) a catalyst containing a titanium compound attached to a solid vaporized magnesium support, and (2) a secondary catalyst containing an organoaluminum compound. However, the catalyst used in FR-B-25 292 11 contains a low content of titanium, which is generally active for paraffin polymerization, especially for ethylene polymerization or copolymerization. In fact, the yield of the prepared polymer or copolymer is very low, and high amounts of titanium components remain. When the catalyst used contains a large amount of titanium, the residual gas content of the polymer or copolymer is higher. * When preparing certain copolymers in the gas phase by this method, the copolymers form more viscous particles. These particles Cohesion into a group. Especially in fluidized bed reactors, it is difficult to avoid the formation of a large number of condensate groups by using such a medium to prepare very low-density linear polyethylenes. This phenomenon will terminate the polymerization reaction. (Please read the precautions on the back before filling in this page) 装 · 线 · Wooden paper standard use SB home standard (CNS) A 4 specifications (210 > < 297 g *)-4-Λ6 B6 20504? V. Description of the invention () (Please read the precautions on the back before filling out this page) A new method for preparing ethylene polymers or copolymers in the gas phase has been discovered. This method uses a highly active catalyst system. Using this catalyst system can overcome or alleviate the problems of the above known methods. In particular, it can produce ethylene polymers or copolymers in high yields and containing very small amounts of catalyst residues. Moreover, this method can produce higher viscosity ethylene copolymers and very low density linear polyethylene in the gas phase without forming agglomerates.
根據本發明在氣相中製備乙烯聚合物或製備含高於80 %重量百分率之乙烯與少於20%重量百#之一種或多種 3至12値碩原子之α-烯烴所聚合的共此方法之 特擻在於： I (1) 此方法健用戚格勒-纳他型觸媒，其是由氛化鎂支持體 以不 $ 原子之 電子供給者化合物D1預活化而形 成包含80%至9 0%莫耳百分率氛化鎂與1 %至2 0%莫 耳百分率D1的支持體.，此支持體為質量平均直徑5至 100«之球狀顆粒，且粒子大小傷如此地分佈，使得質 董平均直徑D·«與數目平均直徑D»的比值小於2 ,以及 令支持體依次與 經濟部中央標準局貝工消费合作社印製 (a) 至少一個含不安定氫原子之電子供給者化合 物Da ; (b) 為一芳香族酸酯之電子供給者化合物D=* ; (c) 四氯化鈦等接觸，然後利用至少一次洗滌操作以去 除過董未被浸漬之四氨化鈦，再將該支持體與 (d) 四氣化鈦接觸。 (2) 該方法包括 5 本紙張尺度逍用中國國家標準(CNS)甲4規格(210x297公釐) A6 B6 20504/ 五、發明説明（） (a) 在第一步驟中，觸媒之預聚合作用是利用將該觸媒 與（i)至少一個含2至12値磺原子之α -烯烴和（ii) 一値含至少一有機金屬化合物（其金靨為週期表上 之第II或第III族元素）之輔觸媒（A)接觸； (b) 在第二步驟中，於流化床反應器中進行一氣相聚合 反應，其傺藉著令預聚合物與乙烯或包含乙烯以及 至少一個含從3至12傾硝廪子之a-烯烴的混合物 接觸，且以如此之接觸，使得乙烯佔待聚合烯烴之 總賭積的80%以上。 根據本發明，第一步驟必須以含觸媒與輔觸媒之觸媒 糸統製備預聚合物。此觸媒包含附在氛化鎂上之特殊支持 體，其使得此觸媒有高量的鈦成分及相當高的乙烯聚合或 共聚合反應活性。此特殊支持體以有機電子供給者化合物 D1預活化，而此化合物D1能大量地存在氣化镁中。此有機 電子供給者化合物D1為人所知為路易士驗，其對於氛化鎂 有相當低之錯合容量。化合物D1是選擇自溫和的錯合劑如 乙醚、硫酸、胺、醯胺、風、亞®和磷化氫。其不能選擇 自能與製備支持體或觸媒之産物反應的藥劑。特別是化合 物D1不能選擇自包含氳原子之電子供給者化合物，如水、 乙酵或酚，或其不能選擇自芳香酸酯。有機電子供給者化 合物D1最好是乙酸。 預活化支持體的組成包含80%至9 9%莫耳百分率之氛 化鎂和1 %至20%莫耳百分率之化合物D1。然而，為了得 到具有高活性且含有高量鈦成分的觸媒，支持體最好包含 (請先閱讀背面之注意事項再填寫本頁) 裝赢 經濟部中央標準局貝工消费合作社印製 各紙張尺度逍用中國B家《準(CHS)甲4規格(210x297公*) -6 - 205047 Λ 6 13 6 五、發明説明（ 經濟部中央標準局貝工消费合作社印製 80%至95%莫耳百分率之氨化鎂和5至20莫耳百分率之化 合物D1。當預活化之支持體包含均質化氣化鎂和化合物D\ 等成分，也就是説，化合物D1從核心到外圍均勻地分佈於 氣化鎂粒子上時，此時觸媒能具有最高活性。為了得到如: 此之預活化支持體，根據沈澱反應的方法，不僅是接觸， 而且製成粉末狀來進行反應。 再者，經發現，預活化支持體使觸媒有很好效果.，且 使其能含高量鈦成分，當支持體為不定形構造時，對.於聚 合過程中所漸增的巨大壓力具有待別的抗性，也就是説， 藉著X-射線繞射分析以確定氣化鎂的结晶型式己大部份或 完全消失。 預活化支持體包括質量平均直徑大約為5〜100徹米 (以）之球狀顆粒，而以直徑為20〜50//之粒子較好。粒子 大小分佈之差異非常小，其質量平均直徑Dm與數目平均 直徑Dn之比值（Dm/Dn)小於2。更特別的是，這些粒子 的粒子大小分佈可以極端的小，例如（i)Dm/D„之比值範 圍為1.1〜1.5(ii)没有或幾乎沒有粒子大小高於1.5X Dw 或低於0 . 6 X D»· (i i i)在同一批粒子大小分佈估量的粒子中 ，超過90%重量百分率的粒子，其直徑大小均在Dm± 10% 之範圍内。 預活化支持賭粒子之比面積（specific surface),可 為 2 0〜10 0m2/g(BET)，而最好是在 30〜6 0n2/g(BET)2 範圍，這些粒子之相對密度可大約在1.2〜2.1的範圍。 在本發明中所利用的預活化支持體可在有機電子供給 (請先閲讀背面之注意事項再填窝本頁) 裝. 線< 私紙張尺度逍用中B困家標準(CNS)甲4規格(210x297公龙） 205047 Λ 6 13 6 五、發明説明（） 者化合物D1存在下，以二烷基鎂化合物與有機氨化物反應 製得。二烷基鎂化合物之化學式可為RifjgR2，其中R1與.R2 可為完全相同或不同之含2至12値磺原子烷基，二烷基鎂 化合物之一重要特性為其可溶於磺氫化合物之基質中，而 支持體之製備亦將在此基質中進行。選擇的有機氮化物是 化學式為R3C1之烷基氮化物，其中R3為2级或最好為含3 至12値磺原子之3级烷基。使用之有機電子供給者化合物 D1最好是化學式為R40Ra之醚類，其中R*和R»是完全相同. 或不同之含1至12個碩原子烷基。 此外，用以製備預活化支持醱的各種反應物必須符合 下列條件： 一 PCl/ITMgR8之莫耳比率為1.5〜2.5。最好在1.95〜 2. 2之間。 -IP/I^MgR8之莫耳比率為0.1〜1.2。最好在0.3〜0 3 之間。 經濟部中央標準局貝工消费合作社印製 (請先閲讀背面之注意事項再填寫本頁) VMgR*與R3C1之間的反應，在有機電子供給者化合物 V存在下，攪拌液態磺氫化合物下是為一沈澱反應。熟於 此技術者均知，此例中，物理因素如基質的黏度，攪拌的 方法與速率及加入反應物之狀況，對於沈澱顆粒之形狀， 結構，粒子大小之分佈均扮演同等重要的角色。然而，為了 得到本發明之可利用的預活化支持體，特別是具有不定形 之結構的支持體，吾人建議沈澱反應在較低溫度範圍10〜 sot：下進行，以10〜50TC較好，而以15〜35¾最好。再者， 吾人建議沈澱反應應緩慢進行，至少超過2小時以上，較好 為1 D〜2 4小時之時間範圍，以使形成的固體産物能夠適當的 本紙張尺本边用中a Η家《準(CNS)甲4規格(210X297公;tt) 8 A6 B6 20504? 五、發明説明（） 組織.持別是當D1化合物大麗插入及其均一的分佈在沈澱 的固體中時。 從上述預活化支持體製備觸媒，包括下列四傾步驟： (a) 利用至少一個含不安定氫原子之電子供給化合物Da, 以處理預活化支持體； (b) 利用至少一為芳香族酸酯之分子内電子供給者化合物 D3,以處理上述所得之支持體； (c) 利用四氣化鈦浸漬支持體，而四氛化鈦的其耳數量好 多於氣化鎂.然後利用液態硪氫化合物至少一次洗滌 操作以去除過量四氛化鈦； (d) 再利用四氣化鈦處理，以活化被浸漬之支持體，然後 最好能用液態碩氫化合物洗支持體。 待別的是，步驟（a)利用含有不安定氳原子之電子供 給者化合物D2以預活化支持程，是為了得到能夠連绩固定 大量四氛化鈦之支持體。實際上此處理包括了有機電子供 給者化合物D1與含不安定氫原子有機電子供給者化合物D2 在預活化支持體進行交換，在此狀況下進行交換，是為了 在實際交換過程中不會改變支持體的結構。特別是化合物 〇2較化合物D1對於氛化鎂有較高且複雜的錯合容量。 含有不安定氫原子之電子供給者化合物Da最好擇自水 ，酵類，酚類，而以含1至12個磺原子之醇類較好。更待 殊的是，化合物卩8可選自乙醇，丙醇，正丁醇，正戊醇， 正己醇。 此方法處理的優點是，如果不用此方法處理，我們將 衣紙張尺度逍用中B B家«準(CNS)肀4規格(210x297公*) (請先閱讀背面之注意事項再填寫本頁) 裝- 經濟部中央標準局貝工消费合作社印製 205047 五、發明説明（） 經濟部中央標準局貝工消費合作社印製 會看到大量支持體的結晶化及不完整的顆粒。特別是本處 理是將預活化支持體與化合物Da接觸，化合物〇8的使用量 為每某耳氮化鎂約用〇 . 2〜1. 2莫耳之化合物Da，而以0.5 〜1.0契耳的Da較好。而且，待別建議此接腾溫度範圍在 〇〜5010，而以10〜351C較好，以進行交換反應而不會改 變起始之預活化支持體。再者，其另一個優點卽，此接觸 在搜拌液態磺氫化合物如正己烷時即可發生。實際上，此 接觸可利用各種可能的方法，例如將在液態硪氫化合物中 之化合物Da於攪拌下加至預活化支持醸之懸浮液中。一般 常見的方法是將此次處理的所有化合物0*固定在支持驩上 ,而支持體的形態與不定形的構造沒有改變。以化合物Da 處理的支持體，在進行下一艏步驟前，可以用液態碩氫化 合物正己烷洗一至數次。 在步驟（b)中，電子供給者化合物D3為芳香族酸醋， 其擇自乙基苯，甲基對位_、甲苯，二丁基或二異丁基酞酸 鹽。此處理利用芳香族酸 1在作用條件支持體的形態 及構造沒有改變。待別是本步驟是以支芳香族酸酯接 觸進行作用，酯類的用量為毎莫耳氣化鎂用0.1〜1.0莫耳 酯類，而以0.2〜0.8莫耳之範圍用量較好。吾人建議此接 觸之溫度範圍大約在10〜60¾而以20〜5GT較好，以使支 持體的形態不會發生改變。此接觸在液態的硪氫化合物如 己烷中》於攪拌下進行較為有利。實際上.此接觸可以各 種可能的方法進行，特別是將在液態硝氫化合物中之芳香 族酸酯於攪拌下加入支持髏懸浮液中。假如適當的話，支 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂_ -線< 本纸張尺度逍用中B國家樣準(CNS)甲4規格(210X297公《) -10 - Λ6 Β6 20504; 五、發明説明（） 持體在進行下一步驟前可用液態的硝氫化合物如正己烷沖 洗一至數次。 在步驟（C)以芳香族酸酯類處理所得之支持體，用四 氛化鈦加以浸漬，四氣化鈦可以單獨使用或在液態磺氫化 合物的溶液中使用。典型的浸漬作用是將支持藤與四氨化 鈦接觸，四氰化鈦之用量為毎莫耳氛化鎂用2其耳至20莫 耳四氣化鈦，而以5某耳至15莫耳四氯化鈦較好。另外， 吾人建議浸漬作用猫度應在5〜120ΊΟ的範圍進行，而以70 V.W: 〜loot：較好，的是在使支持體能保持不定形構造 ，以增強其抵抗應中所增加的壓力。且浸漬作用在 液態磺氫化合物如正己烷中於攪拌下進行是有利於反應之 進行。實際上，浸潰作用可以各種可能的方式進行，特別 是將在液態硪氫化合物中之四氣化鈦於攪拌下加入支持體 懸浮液中。已飽和之支持體在進行下一步驟前，用液態磺 氫化合物洗一至數次，以去除過里未被浸漬到支持體上的 四氛化鈦。 於步驟（c)製得之支持體，在步驟（d)中以四氛化鈦活 化處理。此處理包括將被鈦浸漬的固體與四氣化鈦接觸， 此可單獨或在液態磺氫化合物如正己烷中行，四氧化钛的 用量為每某耳氣化镁用2〜20契耳之四氣化鈦，而以5〜15 莫耳四氮化鈦用量較好。建議此接觸之最適反應溫度為20 〜1201C,而以70〜1201C較好。在液態磺氳化合物如正己 烷中，於攪拌下進行活化步驟最為有利。實際上，此接觸 可以各種可能之方式進行，特別是在液態硪氳化合物中， 各紙張尺度逍用中a國家揉準(CNS)甲4規格(210X297公«) (請先閱讀背面之注意事項再填寫本頁‘)According to the present invention, a method for preparing an ethylene polymer in the gas phase or preparing a polymer containing more than 80% by weight of ethylene and less than 20% by weight of one or more α-olefins with 3 to 12 valence atoms The special features are: I (1) This method uses the Ziegler-Natta type catalyst, which is pre-activated by an oxidized magnesium support with an electron donor compound D1 that does not contain atoms to form 80% to 9%. 0% molar percent magnesium oxide and 1% to 20% molar percent D1 support. This support is a spherical particle with a mass average diameter of 5 to 100 «, and the particle size is so distributed that the quality The ratio of Dong's average diameter D · «to the number average diameter D» is less than 2, and the support is printed in sequence with the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (a) At least one electron donor compound Da containing unstable hydrogen atoms ; (b) Electron donor compound D = * which is an aromatic acid ester; (c) Contact with titanium tetrachloride, etc., and then use at least one washing operation to remove titanium tetraammonium which has not been impregnated by Dong, and then The support is in contact with (d) tetra-vaporized titanium. (2) The method includes 5 paper scales to use Chinese National Standard (CNS) A4 specifications (210x297 mm) A6 B6 20504 / V. Description of invention () (a) In the first step, the pre-polymerization of the catalyst The function is to use the catalyst with (i) at least one α-olefin containing 2 to 12 sulfonate atoms and (ii) one organometallic compound (whose gold is the second or third on the periodic table) Group element) auxiliary catalyst (A) contact; (b) In the second step, a gas-phase polymerization reaction is carried out in a fluidized bed reactor, which is made by prepolymer with ethylene or containing ethylene and at least one The mixture of a-olefins containing 3 to 12 nitriles is contacted, and the contact is such that ethylene accounts for more than 80% of the total gambling volume of olefins to be polymerized. According to the present invention, the first step must be to prepare a prepolymer with a catalyst system containing a catalyst and an auxiliary catalyst. The catalyst contains a special support attached to the oxidized magnesium, which makes the catalyst have a high amount of titanium and a relatively high ethylene polymerization or copolymerization activity. This special support is pre-activated with the organic electron donor compound D1, and this compound D1 can be present in large amounts in vaporized magnesium. This organic electron donor compound D1 is known as the Lewis test, and it has a relatively low mismatching capacity for magnesium oxide. Compound D1 is selected from mild complexing agents such as diethyl ether, sulfuric acid, amines, amides, feng, Ya® and phosphine. It cannot be selected from agents that can react with products that make supports or catalysts. In particular, the compound D1 cannot be selected from electron donor compounds containing radium atoms, such as water, ethyl acetate or phenol, or it cannot be selected from aromatic esters. The organic electron supplier compound D1 is preferably acetic acid. The composition of the pre-activated support comprises 80% to 99% mole percent magnesium oxychloride and 1% to 20% mole percent compound D1. However, in order to obtain a catalyst with high activity and high titanium content, the support should preferably contain (please read the precautions on the back before filling in this page). Zhuangying Printing Paper Standard Xiao uses China ’s “CHS” Grade 4 specifications (210x297 g *) -6-205047 Λ 6 13 6 V. Description of invention (printed by 80% to 95% Mohr by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Percentage of magnesium amide and 5 to 20 mole percent of compound D1. When the pre-activated support contains homogeneous components such as vaporized magnesium and compound D \, that is to say, compound D1 is evenly distributed in the gas from the core to the periphery When the magnesium oxide particles are on, the catalyst can have the highest activity at this time. In order to obtain the pre-activated support like this, according to the method of precipitation reaction, not only contact but also powder to carry out the reaction. Furthermore, it was found The pre-activated support has a good effect on the catalyst, and it can contain a high amount of titanium components. When the support is an amorphous structure, it has resistance to the huge pressure that is increasing during the polymerization process. Sex, that is, Through X-ray diffraction analysis to determine that the crystallized type of vaporized magnesium has mostly or completely disappeared. The pre-activated support includes spherical particles with a mass average diameter of about 5 ~ 100 metre (and more), and the diameter Particles of 20 ~ 50 // are better. The difference in particle size distribution is very small, and the ratio of the mass average diameter Dm to the number average diameter Dn (Dm / Dn) is less than 2. More particularly, the particle size distribution of these particles Can be extremely small, for example (i) The ratio of Dm / D „is in the range of 1.1 ~ 1.5 (ii) No or almost no particle size is higher than 1.5X Dw or lower than 0.6 XD» · (iii) in the same batch of particles Among the particles whose size distribution is estimated, the particles whose diameter exceeds 90% by weight have a diameter within the range of Dm ± 10%. The specific surface area of the pre-activation support particles can be 2 0 ~ 10 0m2 / g (BET), and preferably in the range of 30 ~ 6 0n2 / g (BET) 2, the relative density of these particles can be in the range of about 1.2 ~ 2.1. The pre-activated support used in the present invention can be Supply (please read the precautions on the back before filling the nest page) Pack. Thread < For paper scales, the standard of the B-sleepy family standard (CNS) A4 (210x297 male dragon) 205047 Λ 6 13 6 V. Description of the invention () In the presence of compound D1, it is prepared by reacting a dialkyl magnesium compound with an organic ammonia The chemical formula of dialkylmagnesium compound can be RifjgR2, where R1 and .R2 can be identical or different alkyl groups containing 2 to 12 sulfonate atoms, one of the important characteristics of dialkylmagnesium compounds is their solubility in sulfohydrogen The matrix of the compound, and the preparation of the support will also be carried out in this matrix. The selected organic nitride is an alkyl nitride having the chemical formula R3C1, wherein R3 is a second-order or preferably a third-order alkyl group containing 3 to 12 sulfon atoms. The organic electron donor compound D1 used is preferably an ether of the chemical formula R40Ra, where R * and R »are completely the same. Or different ones contain alkyl groups with 1 to 12 atoms. In addition, the various reactants used to prepare the pre-activated support must meet the following conditions:-The molar ratio of PCl / ITMgR8 is 1.5 to 2.5. Preferably between 1.95 ~ 2.2. -The molar ratio of IP / I ^ MgR8 is 0.1 to 1.2. It is preferably between 0.3 ~ 0 3. Printed by Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) The reaction between VMgR * and R3C1 is in the presence of organic electron supplier compound V, under the stirring of liquid sulfohydrogen compounds. It is a precipitation reaction. Those skilled in the art are aware that in this case, physical factors such as the viscosity of the matrix, the method and rate of stirring, and the state of the added reactants play an equally important role in the shape, structure, and particle size distribution of the precipitated particles. However, in order to obtain the pre-activated support that can be used in the present invention, especially the support with an amorphous structure, we suggest that the precipitation reaction is carried out at a lower temperature range of 10 ~ sot: preferably 10 ~ 50TC, and 15 ~ 35¾ is the best. Furthermore, I suggest that the precipitation reaction should be carried out slowly, at least over 2 hours, preferably within a time range of 1 D ~ 24 hours, so that the solid product formed can be properly used in this paper. Standard (CNS) A 4 specifications (210X297 g; tt) 8 A6 B6 20504? V. Description of the invention () Organization. The difference is when D1 compound Dahlia is inserted and uniformly distributed in the solids of Shendian. The preparation of the catalyst from the above pre-activated support includes the following four-tilt steps: (a) use at least one electron containing an unstable hydrogen atom to supply compound Da to treat the pre-activated support; (b) use at least one of aromatic acids The electron donor compound D3 in the molecule of the ester is used to process the support obtained above; (c) The support is impregnated with titanium tetravaporide, and the number of ears of titanium tetrachloride is better than that of magnesium vapor. Then the liquid hydrogen is used The compound is washed at least once to remove excess titanium tetrachloride; (d) The titanium tetravaporide treatment is then used to activate the impregnated support, and then it is best to wash the support with liquid hydrogen compounds. In addition, step (a) uses the electron donor compound D2 containing unstable diatomic atoms to pre-activate the support process in order to obtain a support that can continuously fix a large amount of titanium tetrachloride. In fact, this process includes the exchange of the organic electron donor compound D1 and the organic electron donor compound D2 containing unstable hydrogen atoms in a pre-activated support. In this case, the exchange is performed so that the support will not be changed during the actual exchange process. The structure of the body. In particular, compound 〇2 has a higher and complex complexing capacity for magnesium chloride than compound D1. The electron donor compound Da containing unstable hydrogen atoms is preferably selected from water, enzymes, and phenols, and alcohols containing 1 to 12 sulfonic atoms are preferred. More specifically, the compound Y8 may be selected from ethanol, propanol, n-butanol, n-pentanol, and n-hexanol. The advantage of this method is that if you do not use this method, we will use the BB standard «quasi (CNS) 肀 4 specifications (210x297 g *) (please read the precautions on the back before filling this page) -Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 205047 V. Description of the invention () Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy will see a large number of crystals and incomplete particles of the support. In particular, in this treatment, the pre-activated support is contacted with the compound Da, and the amount of the compound 〇8 used is about 0.2 to 1.2 moles of the compound Da per certain ear of magnesium nitride, and 0.5 to 1.0 Da is better. Furthermore, it is recommended that the temperature range of this connection be in the range of 0 to 5010, preferably 10 to 351C in order to carry out the exchange reaction without changing the initial pre-activated support. Moreover, another advantage is that this contact can occur when searching for liquid sulfohydrogen compounds such as n-hexane. In fact, this contact can utilize various possible methods, for example, adding the compound Da in the liquid hydrogen compound to the suspension of the pre-activated support with stirring. Generally, the common method is to fix all the compounds 0 * treated on the support, and the shape of the support and the amorphous structure have not changed. The support treated with compound Da can be washed with liquid hydride n-hexane one to several times before proceeding to the next bow step. In step (b), the electron donor compound D3 is an aromatic vinegar selected from ethylbenzene, methyl para-, toluene, dibutyl or diisobutyl phthalate. This treatment utilizes the aromatic acid 1 to support the morphology and structure of the support without changing the conditions. It is to be noted that this step is effected by the contact of branched aromatic acid esters. The amount of esters is 0.1 to 1.0 mol esters for each mole of vaporized magnesium, and the amount in the range of 0.2 to 0.8 mol is better. I suggest that the temperature range of this contact is about 10 ~ 60¾ and 20 ~ 5GT is better, so that the shape of the support will not change. This contact is more advantageously carried out with liquid hydrogen compounds such as hexane under stirring. In fact, this contact can be carried out in various possible ways, in particular, the aromatic acid ester in the liquid nitrohydrogen compound is added to the supporting skull suspension with stirring. If appropriate, please support (please read the precautions on the back before filling in this page) Binding · Order _ -Line < This paper standard is used in China National Standard (CNS) A 4 specifications (210X297) "-10 -Λ6 Β6 20504; 5. Description of the invention () Before proceeding to the next step, the holder can be rinsed with liquid nitrile compounds such as n-hexane one to several times. In step (C), the resulting support is treated with aromatic acid esters and impregnated with titanium tetrachloride, which can be used alone or in a solution of liquid sulfohydride. The typical impregnation effect is to contact the support rattan with titanium tetraammonium. The amount of titanium tetracyanide is molol magnesium oxide. 2 mol to 20 mol titanium tetrahydride, and 5 mol to 15 mol Titanium tetrachloride is preferred. In addition, I suggest that the cat degree of impregnation should be in the range of 5 ~ 120ΊΟ, and 70 V.W: ~ loot: It is better to keep the support in an indefinite structure to enhance its resistance to the increased pressure during stress. And the impregnation is carried out in a liquid sulfohydrogen compound such as n-hexane under stirring is conducive to the reaction. In fact, the impregnation can be carried out in various possible ways, in particular, the titanium tetraoxide in the liquid hydrogen compound is added to the support suspension with stirring. Before proceeding to the next step, the saturated support is washed with liquid sulfohydrogen compound one to several times to remove titanium tetrachloride which has not been impregnated on the support. The support prepared in step (c) is activated with titanium tetrachloride in step (d). This treatment includes contacting the titanium-impregnated solid with titanium tetra-vaporization, which can be performed alone or in a liquid sulfohydrogen compound such as n-hexane. For vaporization of titanium, 5 to 15 mol titanium tetranitride is preferred. It is suggested that the optimum reaction temperature for this contact is 20 ~ 1201C, and 70 ~ 1201C is better. In liquid sulfonium compounds such as n-hexane, it is most advantageous to perform the activation step with stirring. In fact, this contact can be carried out in various possible ways, especially in the liquid 氪 氲 compound, the various paper sizes are used in a national standard (CNS) A 4 specifications (210X297) (Please read the notes on the back first Fill this page again ')
經濟部中央標準局员工消費合作社印製 11 20504? Λ 6 Β6 經濟部中央標準局負工消费合作社印製 五、發明説明（） 將四氮化鈦加入被鈦浸潰之固睡懸浮液中，並播拌0.5〜 10小時以保持混合，而以攪拌1〜4小時較佳。如此處理後 ,固體最好以液態碩氫化合物如正己烷洗一至數次。此種 活化的處理可包括一個或更多此類型的接觸操作。如此處 理，支持體每莫耳的錢可含有4〜10莫耳百分率的鈦。如 此獲得的觸媒與EP-A-336545所描述之觸媒相似。 依照本發明製備聚合物所使用的觸媒条統，.除了上述 之觸媒外，尚包含輔觸媒（A),輔觸媒（A)是選自其金屬為 週期表上第II、III族元素之有機金羼化合物，例如有機 鋁、有機鎂或有機鋅化合物。在有機鋁化合物中有一種或 更多的有機鋁化合物，其化學式為A1R3,其中R為含1〜8 値碩原子的烷基，例如，三乙基鋁，三-異丁基鋁，三-正 己基鋁和三-正辛基鋁。 輔觴媒（A)與存在觸媒中之鈦的相對莫耳量，相當於 輔觸媒（A)中的金屬與觸媒中鈦金屬的荚耳比率，此比率 變化範圍為1〜10,而以2〜5之比率較佳。事實上，當此 比率更低時，觸媒糸統的活性將減弱，此現象己被注意。 第一步驟之»媒条統可任意包含外部電子供給者化合 物D4,其可選自芳香族酸酯類和有機矽化合物如硅烷類的 衍生物。特別是它可以為乙基苯，甲基對位-甲苯或苯基 三乙氣硅烷。外部電子供給者化合物與輔觸媒（A)的莫耳 比率至少為0.1且不超過0.8,而以接近0.3為較佳。過量 的化合物Μ將滅弱觸媒条統的活性。一般認為觸媒条統中 完全不含外部霣子供給化合物較好，特別是在製備乙烯鹼 (請先閲讀背面之注意事項再填寫本頁) 裝- 訂· 線. 本紙張尺度通用中困國家橾準(CDS)甲4規格(210x297公*) 12 - 經濟部中央標準局貝工消费合作社印製 205047 A6 __B6_ 五、發明説明（） 基預聚合物的時候。 根據此發明，在第一個步费[中，預聚合物以至少一個 含2〜12値磺原子之α-烯烴聚合製備而成。此α-烯烴可 遘自乙烯.丙烯，1-丁烯，卜己烯，4-甲基-1-戊烯，1-辛烯和1-十二磺烯。然而，較好是以乙烯或丙烯單獨聚合. 成預聚合物，或以至少含80%其耳百分率的α-烯煙混合 物聚合，而以90某耳百分率之乙烯或丙烯聚合較佳。.此預、 聚合步驟可以一個步驟或連缠幾値步驟進行，當每毫襄耳 鈦含0.1〜500克，較好含10〜400克，更好為含150〜300 克之預聚合物，則預聚合反應會停止。 預聚合物可依已知之方法製備，例如它可在飽和的液 態磺氫化合物如正-己烷，正-庚烷的懸浮液中製備，溫度 範圍為20〜801C,而以30〜65*C較佳。再者，在反應器中 ，預聚合物可以在氣相中以機械提拌及/或流化床反應器 製備，溫度範圍為10〜60C,以25〜40%較佳，而總壓力 範圍為0.1〜5MPa。假如欲利用丙烯製備預聚合物，則可 在液態丙烯的懸浮液中，溫度範圍〇〜較好為10〜 301下進行。無論利用什麽方法製備預聚合物，為控制預 聚合物的數量，預聚合反應速率必須相當緩慢的進行。此 速率為每毫莫耳的含钛觸媒每小時作用低於或等於150克 的烯烴，此速率可因預聚合作用的溫度或《媒與輔觸媒 (A)的相對量而改變。 依據本發明影锻預聚合反應之主要因素為維持預活化 支持體的球形構造，不改變粒子大小的分佈，裂備優良之 (請先閲讀背面之注意事項再填寫本頁) 裝. 訂_ 線< 本紙張尺度逍用中國困家榣準(CNS)甲4規格(210x297公*) - 13 - 2〇5〇4· Λ6 Β6 經濟部中央標準局貝工消費合作社印製 五、發明説明（） 預聚合物及改進氣相聚合反應的連鑛步驟的待性。此預聚 合物改良的性質及優點是有蘭於在連績聚合過程中粒子對 於巨增的壓力具有優良的機械力，以抵抗磨擦及破，裂。此 外，本發明之另一個驚人的優點是其製成的預聚合物，其_ 為粉末狀、非粘滯性顆粒。此預聚合物粉末有很好的流，體 性質，所以很容易使用於連缅的聚合作用。而且，當预聚 合物在懸浮液中被製備，我們發現溶於液體中的預聚合物 非常少，此提供了另一痼巨大的優點，即預聚合物可避免 萃取及冲洗的操作。因此，懸浮液的預聚合物可以直接進 入第二步驟。 在第二步驟的方法中，是將先前製備得的預聚合物與 乙烯或與含乙烯以及至少一含3至12値碩原子之α-烯烴 的混合物接觸，以進行聚合反應，其中α-烯烴可選自丙 烯，1-丁烯，4-甲基-1-戊烯，1-己烯，卜辛烯，1-癸烯 ，及1-十二碩烯。大部份的情況是單次乙烯或以含乙烯與 卜丁烯或4-甲基-戊烯混合物聚合。聚合時使用的烯烴是 存在於氣酵[的混合物中，混合物中乙烯至少佔80%的全部 烯烴體積。製造線型非常低密度或線型低密度的聚乙烯時 ,乙烯與烯烴的相對暖稹比率分別為8 0〜9 0 %及9 0〜9 6 % 。乙烯或是氣體混合物可含有如氮，乙烷，丙烷，異戊烷 等鈍氣和如氫氣之鍵長限制劑。實際上氣相聚合反應是在 流化床的反應器中進行，形成的聚合物或共聚物的顆粒藉 著平行向上由壓縮機打入的氣體；在反應器中保持流化狀 態，其速度為最小流化速度的2〜10倍，而以5〜8倍較佳 (請先閲讀背面之注意事項再填寫本頁) 裝- 訂- 線. 本紙張尺度遑用中國Η家樣毕(CNS)甲4規格(210X297公*) - 14 - Λ6 B6 205047 五、發明説明（ 先 閲 讀 背 面 之 注 意 事 '項 再 填 寫 本 頁 。為了提高聚合反應所形成的熱之移除效率及避免凝聚的 形成，流化速度愈高愈好，但其受限於設備裝置，如壓縮 機的最大容置和反應器的大小。一般而言，流化速度在15. 〜80公分/秒，而以高於4〇^分/秒較佳。氣流離開流化 床反應器經過冷卻条統為了g餘聚合反應或共聚合反應 之反應熱，然後壓縮機再將其送入流化床反應器再循環。 聚合反應之反應器中之平均壓力接近大氣壓力，但為了增.. 加聚合速率，以較大氣壓力高之壓力較好，其範圍約在 0.1〜5MPa,以0.2〜2MPa較佳。反應溫度須低於産品的软 化溫度，一般在0〜120Τ的範圍，而以50〜901C為佳。聚 合速率可依反應溫度及/或預聚合物的使用量而改變。 經濟部中央標準局貝工消費合作社印製 實際上，進行氣相聚合反應時，預聚合物被加入聚合 反應器中是為了使其與乙烯或含烯烴之氣體混合物進行聚 合。預聚合物是以乾粉末狀或液態磺氫化合物懸浮液的形 式加入反應器中，其可以連缠式或間斷式加入反應器中， 預聚合物可以輔觸媒（Β)活化，其是完全相同或不同於輔 觸媒（Α)。輔觸媒（Β)可為有機鋁化合物如三烷基鋁或鹵化 烷基鋁或兩者之混合物。特別是它可以選自三乙基鋁，三 -正丙基鋁，三-異丁基鋁。其可依任何所知道的方法加入 聚合反應器中，如單獨加入、或以一種或多種烯烴或飽和 親油性碩氫化合物稀釋後加入。共觸媒（Β)可以液態或完 全轉化為氣態加入聚合反應器中，特別是當它具有高度揮 發性時。利用輔觸媒（Β)活化預聚合物可以在預聚合物加 入聚合反應器前進行，特別可在預聚合物加入導管之前進 本紙張尺度逍用中國國家樣準(CNS)甲4規格(210x297公龙) 15 20504? Λ 6 Β6 五、發明説明（ 經濟部中央標準局貝工消費合作社印製 行。 輔觸媒（B)的使用董為輔觸媒（B)中之金屬與預聚合物 中的鈦金属莫耳比率在.0.5〜100的範圍，而以1〜20較 佳。 除了辅觸媒（B)外，電子供給者化合物π亦可利用， 其與D3, D«可完全相同或不同。在預聚合物加入聚合反應 器或共聚合反應器之前，將化合物De加入預聚合物中是有 益的。其可單獨加入反應器中或與輔觸媒（B)混合加入。 輔觸媒（B)與化合物D»的莫耳比率為5〜100 。 利用本發明的方法，可在工業生産條件下，製造大量 可再生性的乙烯聚合物或共聚物。例如可能製備相對密度 高於Q . 94之所謂高密度聚乙烯，其中乙烯同質聚合物及乙 烯與含3至12掴碳原子之一種或多種α -烯烴所形成之共聚 物佔絶大多數。亦可能製備相對密度在0 . 9 10至0 . 94 0之間 的線型低密度聚乙烯，其含有乙烯與3至12個磺原子之一 種或多種α-烯烴所形成之共聚合物，其中乙烯衍生單元 重量含量佔90〜96%。 此方法可能製備持定密度範圍在0.880至0 . 91 0間之線 型非常低密度聚乙烯，其含有乙烯與3至12痼磺原子之一 種或多種烯烴所形成之共聚物，其中乙烯衍生單元重量含 量高於80%低於90%。這些非常低密度聚乙烯有一値融解 指數（ΜΙ2),其是在2公斤裝，1901C下測定，其值範圍為 每10分鐘0.1至10克。這些非常低密度聚乙烯有非常粘稠 的傾向，利用己知技術在流化床反應器中製備此類聚合物 η 先 閲 讀 背 φ 之 注 意 事 項 再 填 寫. 本 頁 裝 訂 線 本紙張尺度逋用中Β Η家標準(CNS)甲4規格(210X297公*) -16 Λ 6 Β6 20504· 五、發明説明（） ，亦具有上述之問題。本發明最大的優點即是克服上述的 問題或至少減輕此問題。 依據本發明製備的非常低密度聚合物亦可用於任何此 類聚合物己知的應用中。而且，依據本發明所製成之聚合 物經發現對於電線電纜方面之應用非常有用。此聚合物能 夠單獨或與其他聚合物混合使用。對於中、高電壓電嫌線 的絶緣，此聚合物亦可利用氧化物過為交叉連接麵，進行 交叉連接，卽可絶緣。 本發明的方法其優點在以具有非常高效率之觸媒製備 乙烯聚合物或共聚物，結果其含有非常低的鈦含量，特別 是低於5 PPH,和低含量的氮元素，待別是低於ΙΟΟρρΒ。 另一個有利的發現是在聚合反應過程中，聚合物或共 聚物顆粒的進展是均一的，結果得到球狀之聚合物或共 聚物顆粒。共聚物顆粒之質量平均直徑D»的範圍為250〜 1000m,及具有非常狹窄之粒子大小分佈，其D»與數目平 均直徑的比值小於3 ,以小於2較佳。此顆粒成球形的 好處是使得可能製備乙烯聚合物或共聚物，特別是能製備 更多的線型非常低密度之粉末狀聚乙烯，其具有非常好的 流動性，且無凝聚的現象。此粉末明顯的為高密度，特別 是在0.35〜0.50(^/^〇3的範圍。 涣宙聚会物或共聚物粉支的铒流動袢 . 聚合物或共聚物粉末的可流動性可藉由形狀為沒有尖 角、體積為0.286公升的圓錐漏斗型入口測得，此圓錐具 有垂直的軸及頂角朝下，小底部直徑為10厘米，大底部直 冬紙»尺度遑用中國Η家樣準(CNS)甲4規格(210X297公釐）_ 17 - (請先閱讀背面之注意事項再填寫本頁) -裝- 線. 經濟部中央標準局員工消费合作社印製 όβ6 205047 五、發明説明（） 徑為93厘米，高為113厘米。 漏斗的開口可以玻璃片關閉。聚合物或共聚物粉末事 先弄鬆散，由上部的G傾倒入漏斗中。當漏斗缜滿時，過 量的粉末以水平地掃除，使其與漏斗上面的孔平齊。玻璃 片關閉下面的孔然後移開.，確定是否有粉末的流出。粉末 的流動性是以漏斗中的粉末完全流空所需的時間來決定。 依據此方法，粉末流空時間少於25秒則可視為流動性很好 ，假如粉末流空的畤間超過35秒，則此流動性算是很差。 •决宙粒罕皙g平均首，描JUJS教目平均盲撺Dn的方法 根據本發明，支持體或觸媒粒子的質量平均直徑L和 數目平均直徑0„是藉由[^1〇1113<影像分析儀（《1(；1：〇16&51^ ements Ltd, Great,Brita.in)的顯徹鏡觀察而測得。測量 的原理包括利用光學顯徹鏡實驗研究粒子組群，頻率表是 將屬於毎一類（i)直徑的粒子，給定一痼數字（ni),毎一 類i的持性由上逑包含於所分類的中間值直徑（di)表之。 依據1981年6月法國標準NFX 1 1-6 3 0所提供1)„1和011的公式 如下： Σ ni(di)3di 質量平均直徑：D«=- Σ ni(di)3 Σ nidi 數目平均直徑：Dm=- Σ ni D«/Dn的比值表示粒子大小的分佈，有時亦稱為’‘粒 子大小分佈寬度”。利用Optoniax影像分析儀的測量方法 是藉著轉變顯微鏡的放大倍率16〜200倍，觀察支持髏或 (請先閱讀背面之注意事項再填寫本頁) 裝- -線· 經濟部中央標準局貝工消費合作社印製 本紙張尺度遑用中Η困家標準(CNS)甲4規格(210x297公釐） _ ^ g〇5〇^r· Λ 6 B6 經濟部中央標準局貝工消费合作社印製 五、發明説明（） 觸媒粒子的懸浮液。電視攝影機利用轉變顯微鏡挑取影像 ，並將挑取之影像輸入電腦，電腦一線一線，—點一點的 分析影像，以測量粒子的向度或直徑，然後將其分類。 下面的例子將説明本發明： m 1 剪備栢活彳h本拮88 : 10. 2公升的混合物中包含10莫耳在正-己烷中之二-丁 基鎂，6.45公升的正-己烷及最後的1公升二異戊醚等. 在第一步驟於室溫25亡，含氮氣下，連鑛加入於30公升 不锈鋼反應器中，此反應器具有每分鐘600轉的旋轉速度 的攪拌糸統及一外殼。第二步驟中，攪拌条統的速度維持 在每分鐘60 0轉及反應器中溫度維持25它，2.4公升特丁基 氣加入混合物中，以固定的轉速維持12小時。時間到了以 後，混合物在2’51〇維持3小時。得到的沈澱以15-公升正_ 己烷沖洗。重復沖洗沈澱6次。得到的固體産物為預活化 支持體（Α)被植基在氛化鎂上，固體産物相對於氮化镁含1 2其耳百分率的二異戊醚。當以顯徹鏡檢査，預活化支持 醱（Α)以球形顆粒的形式存在，其具有21«的質量平均直 徑和相當窄的粒子大小分佈，例如粒子的Dm/ 〇„大小比率 相當於1.4。預活化支持體（A)的比面積大約為45i2/g (BET)。氛化鎂在預活化支持賭的構造完金為不定型。 12 I 馳11 由例1製備得之預活化支持體（A)的懸浮液包含 升正烷中之4莫耳的氣化鎂，預活化支持體（A)在氮氣下 加入於30公升的不锈銷反應器中，此反應器裝有每分鐘 (請先閲讀背面之注意事項再填寫本頁) < 裝· 訂 本紙張尺度逍用中國國家標準(CNS)甲4規格(210x297公釐） _ 19 _ 2〇5〇4· A 6 Β6 經濟部中央標準局貝工消費合作社印製 五、發明説明（） 35 0轉的攪拌糸統。此懸浮液在室溫25υ維持攢拌下，加 入18公升的正-己烷，超過30分鐘的速率下慢慢加入0.365 公升的正-丁醇，在251C,持績攪拌1小時可得到.活化的 支持體懸浮液。時間到後，停止摟拌以使活化支持體沈澱 ，去除上層液，活化支持體於攪拌下再懸浮於6公升的 正-己院中。 在第二步驟中，.1 〇公升的正-己烷邡入於活化支持體 的最後懸#液中，251G下，維持攪拌，接下來以超過30分 鐘之速率慢慢加入4 6公升的乙基苯。處理的支持髏懸浮 液在25Ό下持缠攪拌1小時。時間到後，停止攪拌以使支 持髏沈澱，去除上層液，處理過的支持體在25°C下，每次 以20公升正-己烷.連績洗三次，每次洗時保持懸浮液攪拌 15分鐘，然後再使處理過的支持體沈澱20分鐘，去除上厣 液，使支持體再懸浮，最後將處理的支持體懸浮於6公升 的正己烷中。 在第三步驟中，6公升的四氮化鈦於25t：,攪拌下加 入處理過之支持髏之最後懸浮液中。獲得的懸浮液加熱到 l〇〇°C,在此溫度下持缠攪拌2小時。時間終了，被飽和 的支持體懸浮液攪拌冷卻至50Ό,然後停止攪拌使被飽和 的支持體沈澱，去除上層液，飽和的支持賭在5QTC下，每 次以20公升的正己烷連缠洗三次，然後在25^下，每次 以20公升的正己烷洗二次。最後將被浸漬的支持體（B), 在25TC下，再懸浮於6公升正己烷。球形顆粒一中每痼鎂 原子含有6¾的鈦原子。 (請先閲讀背面之注意事項再塡寫本頁) 裝· 訂_ 線- 各紙張尺度遑用中a B家«準(CNS)甲4規格(210X297公龙) -20 - 2〇5〇β Λ6 Β6 經濟部中央標準局貝工消費合作社印製 五、發明説明（） 在第四傾步驟中，9公升的四氛化鈦於25TC播拌下加 入於被浸漬的支持體（B)的最後懸浮液中，獲得的懸浮液 加熱至1QQO,在此溫度下持缠攢拌2小時。時間到以後 ，獲得的觸媒懸浮液被攪拌冷卻至50°C,然後停止搜拌以 使觸媒沈澱，去除上層液，觸媒在5〇υ下，每次以20公升 的正己烷連鑲洗三次，在25°C下，毎次以20公升的正己院 連缠洗四次0 :、 觸媒（C)在氮氣中被分離及儲存。其每値鎂原.子中含 5.5%的鈦原子，其包含質量平均直徑為21w之球;狀顆粒， 粒子大小分佈D»/Dn比值為1. 4。 (A)#TFR烷躲瘅液Φ餺備丙拢牾聚会物 . 立方米的不锈網反應器中，裝置毎分鐘14 0轉的 旋在601D,保持在氮氣壓力下，連級加入450公 升正己烷、2.05某耳的三-正辛基鋁及在例2製備得之含 0.41莫耳鈦之觸媒（C)及液態的丙烯（以18公斤/小時的 穩定流率加入）。經4小時20分鐘反應終止，反應器排氣 。得到的預聚合物連缅以300公升的正己烷洗3次。反應 器中的物質轉移到乾燥器中，利用熱氪蒸氣蒸發去除正己 烷。得到乾燥之預聚合物（D),其為非粘稠性粉末，具有 下列性質： —鈦含量：25 0 ρρπ -預聚合物（D)中鋁/鈦比率：2 -毎毫莫耳的鈦所得預聚合物的量：190克 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂- 線. 本紙張尺度遑用中國B家樣準(CNS)甲4規格(210X297公*) - 21 - 20504*? Λ6 B6 經濟部中央標準局员工消费合作社印t 五、發明説明（） —視密度：0.330克/立方公分 —粒子質量平均直徑：110 iu。 (in镰型非常飪疮庠聚7.嫌的賻備 此操作是在流化床反應器中進行，其為一直徑0.45公 尺，高7公尺，下部裝置了一個流化格子（fluidization grid)且支撐一痼脱離室之垂直圖柱髏。該反應器裝置有 外部氣體再循環導管連接頂部的莾至反應器的下部位 於流體化格子的下方，且裝置一 環壓縮機及熱傳導· \-厂， 裝置。利用供料導管將本反應氣體混合物之主要組成分如. 乙烯，1-丁烯、氫和®送入流化床，更特別是溢出時可進入 再循琛導管。 反應器之流化床應固定在流化格子上1.8公尺之處， 此流化床中含有7 0公斤線型非常低密度聚乙烯粉末正在形 成。反應器加熱到60它，以0.25公斤/小時之速率加入預 聚合物（D)。 此反應氣體混合物的總壓為1.6MPa且以0.55公尺/秒 的向上流動速率由流化床中升起。其含體積百分率為30% 之乙烯，11%之卜丁烯、12%之氫氣及47%之氮氣。 在這些狀況下，線型非常低密度聚乙烯以15公斤/小 時的速率被製備，其為粉末的形式，有好的流動性，具有 下列之性質： 一比密度：0.900 —由1-丁烯衍生之單位的重量含盪：17.5% —在2公升裝，190t：下測得之融解指數MI2: 1克/10分 (請先閲請背面之注意事項再填.寫本瀆) -裝· 訂- 線· 本紙張尺度通用中8國家標準(CNS)甲4規格(210x297公*) - 22 - A 6 Β6 2〇5ΰ4? 五、發明説明（） 鐘 (請先閲讀背面之注意事項再填寫本頁) —視密度：0.390克/立方公分 -欽_含量：4ρρ· 一粒子質量平均直徑D« : 430 W -Dn/ Dn 比值：1.6 一流動性：20秒 m 4 (A)存TF R烷鶼择液中丙烯指聚会物的靱備： 在1立方公尺不锈钢反應器中，其裝有毎分鐘140轉 的旋轉攛拌裝置，在60TC ，維持氮氣壓力下，連缅加入 450公升的正己烷、1.09莫耳的三乙基鋁、0.545莫耳的氰 化二乙基鋁、少置的例2所製備得的觸媒（C)(其中含0.41 莫耳鈦）及液態丙烯（其加入速率為18公斤/小時）。經4 小時又20分鐘後，停止加入丙烯，反應器排氣，所得預聚 合物以300公升正己烷連鑛洗三次，將反應器中的物質移 入乾燥器中，以熱氮蒸氣蒸發去除正己烷。 在此條件下可得一非粘稠性粉末狀預聚合物（E),其 具有下列特性： 經濟部中央標準局貝工消费合作社印製 一钛含童：26〇ppb 一乾燥的預聚合物（E)中鋁/鈦之比率：1.2 —每毫莫耳的鈦可得預聚合物的量：185克 一視密度：0.46克/立方公分 (R)镰型飪密麻聚烯夕鄴備： 此在流化床反應器中的操作與例3-Β相同。此反應器 本紙張尺度逍用中國Η家標準(CNS)甲4規格(210x297公釐) 23 -Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 11 20504? Λ 6 Β6 Printed by the Consumer Work Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention Mix and mix for 0.5 ~ 10 hours to keep mixing, and it is better to stir for 1 ~ 4 hours. After such treatment, the solid is preferably washed one to several times with a liquid hydrogen compound such as n-hexane. Such activation treatment may include one or more contact operations of this type. As stated here, the support may contain 4-10 mole percent titanium per mole. The catalyst thus obtained is similar to that described in EP-A-336545. The catalyst system used in the preparation of the polymer according to the present invention, in addition to the above-mentioned catalysts, also contains the auxiliary catalyst (A), the auxiliary catalyst (A) is selected from the metals of the periodic table II, III Group of organic gold compounds, such as organic aluminum, organic magnesium or organic zinc compounds. Among the organoaluminum compounds, there are one or more organoaluminum compounds, the chemical formula of which is A1R3, where R is an alkyl group containing 1 to 8 large atoms, for example, triethylaluminum, tri-isobutylaluminum, tri- Aluminum n-hexyl and aluminum tri-n-octyl. The relative molar amount of the auxiliary catalyst (A) and the titanium present in the catalyst is equivalent to the ratio of the metal in the auxiliary catalyst (A) to the titanium in the catalyst. This ratio varies from 1 to 10. The ratio of 2 to 5 is better. In fact, when this ratio is lower, the activity of the catalyst system will weaken, and this phenomenon has been noticed. In the first step, the media system can optionally include the external electron supplier compound D4, which can be selected from aromatic acid esters and organosilicon compounds such as silane derivatives. In particular, it can be ethylbenzene, methyl para-toluene or phenyl triethylsilane. The molar ratio of the external electron donor compound to the auxiliary catalyst (A) is at least 0.1 and not more than 0.8, and preferably close to 0.3. Excess compound M will deactivate the activity of the catalyst system. It is generally considered that the catalyst system is completely free of external enzymatic supply compounds, especially in the preparation of ethylene alkali (please read the precautions on the back before filling out this page). Binding-Binding · Line. This paper size is generally used in troubled countries Standard (CDS) Grade 4 (210x297 g *) 12-Printed 205047 A6 __B6_ by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention () based prepolymer. According to this invention, in the first step [, the prepolymer is prepared by polymerizing at least one α-olefin containing 2 to 12 sulfon atoms. This α-olefin can be selected from ethylene. Propylene, 1-butene, hexene, 4-methyl-1-pentene, 1-octene and 1-dodecene. However, it is preferable to polymerize ethylene or propylene alone into a prepolymer, or to polymerize with an α-olefin smoke mixture containing at least 80% of its ear percentage, and it is more preferable to polymerize ethylene or propylene at a 90% ear percentage. . This pre-polymerization step can be carried out in one step or several cascade steps. When each milliliter of titanium contains 0.1 to 500 grams, preferably 10 to 400 grams, more preferably 150 to 300 grams of prepolymer, then The prepolymerization reaction will stop. The prepolymer can be prepared according to known methods, for example, it can be prepared in a saturated liquid sulfohydrogen compound such as n-hexane, n-heptane suspension, the temperature range is 20 ~ 801C, and 30 ~ 65 * C Better. Furthermore, in the reactor, the prepolymer can be prepared in the gas phase by mechanical stirring and / or fluidized bed reactor, the temperature range is 10 ~ 60C, preferably 25 ~ 40%, and the total pressure range is 0.1 ~ 5MPa. If propylene is to be used to prepare the prepolymer, it can be carried out in a suspension of liquid propylene at a temperature ranging from 0 to preferably 10 to 301. No matter what method is used to prepare the prepolymer, in order to control the amount of prepolymer, the rate of the prepolymerization reaction must be carried out relatively slowly. This rate is less than or equal to 150 grams of olefin per millimolar of titanium-containing catalyst per hour. This rate can be changed by the temperature of the prepolymerization or the relative amount of the medium and the auxiliary catalyst (A). According to the invention, the main factor of the shadow forging prepolymerization reaction is to maintain the spherical structure of the pre-activated support, without changing the particle size distribution, and the cracking is excellent (please read the precautions on the back before filling this page). < The size of this paper is easy to use China Sleepless Standard (CNS) Grade 4 (210x297 g *)-13-2〇5〇4 · Λ6 Β6 Printed by Beigong Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs ) Prepolymers and improve the continuity of the gas-phase polymerization reaction ore steps. The improved properties and advantages of this prepolymer are that Yulan has excellent mechanical force against the greatly increased pressure during the continuous polymerization process to resist friction, cracking and cracking. In addition, another surprising advantage of the present invention is that the prepolymer made of it is powdery, non-viscous particles. This prepolymer powder has good fluidity and bulk properties, so it is easy to use for the polymerization of Lien Burmese. Moreover, when the prepolymer is prepared in suspension, we find that there are very few prepolymers dissolved in the liquid, which provides another huge advantage that the prepolymer can avoid extraction and washing operations. Therefore, the prepolymer of the suspension can directly go to the second step. In the method of the second step, the previously prepared prepolymer is contacted with ethylene or with a mixture containing ethylene and at least one α-olefin containing 3 to 12 large atoms to carry out the polymerization reaction, wherein the α-olefin It can be selected from propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, octene, 1-decene, and 1-dodecene. In most cases, it is a single polymerization of ethylene or a mixture of ethylene and butylene or 4-methyl-pentene. The olefins used in the polymerization are present in the gas-fermentation mixture, where ethylene accounts for at least 80% of the total olefin volume. When manufacturing linear very low-density or linear low-density polyethylene, the relative warming ratios of ethylene and olefin are 80 to 90% and 90 to 96%, respectively. Ethylene or gas mixtures may contain passive gases such as nitrogen, ethane, propane, isopentane and bond length limiters such as hydrogen. In fact, the gas-phase polymerization reaction is carried out in a fluidized bed reactor, and the particles of the polymer or copolymer formed are driven upward by the compressor in parallel; the fluidized state is maintained in the reactor at a speed of The minimum fluidization speed is 2 ~ 10 times, and 5 ~ 8 times is better (please read the precautions on the back and then fill out this page) Binding-Ordering-Line. This paper size is not based on Chinese Η 家 样 毕 (CNS) A4 specifications (210X297 g *)-14-Λ6 B6 205047 V. Description of the invention (First read the notes on the back side) and then fill out this page. In order to improve the efficiency of heat removal caused by the polymerization reaction and avoid the formation of condensation, The higher the fluidization speed, the better, but it is limited by the equipment, such as the maximum capacity of the compressor and the size of the reactor. In general, the fluidization speed is 15. ~ 80 cm / sec, and is higher than 4 〇 ^ min / sec is preferred. The gas stream leaves the fluidized bed reactor and passes through the cooling system for the heat of reaction of the residual polymerization or copolymerization reaction, and then the compressor sends it to the fluidized bed reactor for recycling. The average pressure in the reactor is close to atmospheric pressure However, in order to increase the polymerization rate, it is better to use a larger gas pressure and a higher pressure. The range is about 0.1 ~ 5MPa, preferably 0.2 ~ 2MPa. The reaction temperature must be lower than the softening temperature of the product, generally 0 ~ 120T The range is preferably 50 ~ 901C. The polymerization rate can be changed according to the reaction temperature and / or the amount of prepolymer used. Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In fact, when performing gas phase polymerization, The prepolymer is added to the polymerization reactor to polymerize it with ethylene or an olefin-containing gas mixture. The prepolymer is added to the reactor in the form of a dry powder or liquid sulfohydrogen compound suspension, which can be entangled It can be added into the reactor in the form of or intermittently, the prepolymer can be activated by the auxiliary catalyst (B), which is completely the same or different from the auxiliary catalyst (Α). The auxiliary catalyst (Β) can be an organoaluminum compound such as trialkyl Aluminum or alkylaluminum halide or a mixture of both. In particular, it can be selected from triethylaluminum, tri-n-propylaluminum, tri-isobutylaluminum. It can be added to the polymerization reactor according to any known method , If added separately, or One or more olefins or saturated lipophilic hydrogen compounds are added after dilution. The co-catalyst (B) can be added to the polymerization reactor in liquid state or completely converted to gaseous state, especially when it is highly volatile. Use the auxiliary catalyst (B) ) Activation of the prepolymer can be carried out before the prepolymer is added to the polymerization reactor, especially before the prepolymer is added to the conduit into the paper scale. Chinese National Standard (CNS) A 4 specifications (210x297 male dragon) 15 20504? Λ 6 Β6 V. Description of invention (printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Use of the auxiliary catalyst (B) Dong Mo is the ratio of the metal in the auxiliary catalyst (B) to the titanium metal in the prepolymer at .0.5 ~ 100, preferably 1 ~ 20. In addition to the secondary catalyst (B), the electron donor compound π can also be used, which can be identical to or different from D3, D «. Before the prepolymer is added to the polymerization reactor or the copolymerization reactor, it is beneficial to add the compound De to the prepolymer. It can be added to the reactor alone or mixed with the auxiliary catalyst (B). The molar ratio of the auxiliary catalyst (B) to the compound D »is 5 to 100. Using the method of the present invention, a large number of renewable ethylene polymers or copolymers can be manufactured under industrial production conditions. For example, it is possible to prepare so-called high-density polyethylene having a relative density higher than Q.94, in which the copolymers of homopolymers of ethylene and ethylene and one or more α-olefins containing 3 to 12 slap carbon atoms account for the vast majority. It is also possible to prepare a linear low-density polyethylene having a relative density between 0.910 and 0.940, which contains a copolymer of ethylene and one or more α-olefins having 3 to 12 sulfonic atoms, in which ethylene Derivative unit weight content accounts for 90 ~ 96%. This method may produce a linear very low density polyethylene with a fixed density ranging from 0.880 to 0.910, which contains a copolymer of ethylene and one or more olefins of 3 to 12 sulfon atoms, in which the weight of the ethylene-derived units The content is higher than 80% and lower than 90%. These very low-density polyethylenes have a value of melting index (ΜΙ2), which is measured at 1901C in a 2 kg pack, and its value ranges from 0.1 to 10 grams per 10 minutes. These very low-density polyethylenes have a tendency to be very viscous. Use known techniques to prepare such polymers in a fluidized bed reactor. Η Read the precautions on the back φ before filling in. This page is used in binding paper. Β Η home standard (CNS) A 4 specifications (210X297 public *) -16 Λ 6 Β6 20504 · V. Description of invention (), also has the above problems. The greatest advantage of the present invention is to overcome the above-mentioned problem or at least alleviate the problem. The very low density polymers prepared in accordance with the present invention can also be used in any known application for such polymers. Moreover, the polymers made in accordance with the present invention have been found to be very useful for wire and cable applications. This polymer can be used alone or mixed with other polymers. For the insulation of medium and high voltage electrical lines, this polymer can also use oxide as a cross-connecting surface for cross-connecting and can be insulated. The advantage of the method of the present invention is that it produces ethylene polymer or copolymer with a catalyst with very high efficiency. As a result, it contains a very low titanium content, especially less than 5 PPH, and a low content of nitrogen element, unless it is low At ΙΟΟρρΒ. Another advantageous finding is that during the polymerization reaction, the progress of the polymer or copolymer particles is uniform, and as a result, spherical polymer or copolymer particles are obtained. Copolymer particles have a mass average diameter D »ranging from 250 to 1000 m, and have a very narrow particle size distribution. The ratio of D» to the number average diameter is less than 3, preferably less than 2. The advantage of the spherical shape of the particles is that it makes it possible to prepare ethylene polymers or copolymers, especially to produce more linear very low density powdered polyethylene, which has very good fluidity and no agglomeration. This powder is obviously of high density, especially in the range of 0.35 ~ 0.50 (^ / ^ 〇3. Huanzhou gatherings or copolymer powder-supported erbium loop. The flowability of polymer or copolymer powder can be achieved by The shape is measured by a conical funnel-shaped inlet with no sharp corners and a volume of 0.286 liters. The cone has a vertical axis and the apex angle is facing down. The diameter of the small bottom is 10 cm. The large bottom is straight winter paper. (CNS) A4 specifications (210X297 mm) _ 17-(Please read the precautions on the back before filling in this page) -Installation- Line. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy όβ6 205047 V. Description of invention () The diameter is 93 cm and the height is 113 cm. The opening of the funnel can be closed by a glass sheet. The polymer or copolymer powder is loosened in advance and poured into the funnel from the upper G. When the funnel is full, the excess powder is swept horizontally So that it is flush with the hole on the top of the funnel. The glass plate closes the hole on the bottom and then moves away to determine whether there is any powder flowing out. The fluidity of the powder is determined by the time required for the powder in the funnel to completely empty. This method When the powder flow time is less than 25 seconds, it can be regarded as good fluidity. If the powder flow time is more than 35 seconds, the fluidity is very poor. • The average particle size is average, and the average JUJS teaching is average. Method of blinding Dn According to the present invention, the mass average diameter L and the number average diameter 0 of the support or catalyst particles are determined by [^ 1〇1113 < image analyzer (<1 (; 1: 〇16 & 51 ^ ements Ltd, Great, Brita.in). The principle of the measurement includes the use of optical microscope experiments to study the particle group. The frequency table is to classify the particles belonging to each category (i) diameter, given a The numbers (ni), and the persistence of each type of i are included in the table of classified median diameters (di). According to the June 1981 French standard NFX 1 1-6 3 0 provided 1) "1 and The formula for 011 is as follows: Σ ni (di) 3di mass average diameter: D «=-Σ ni (di) 3 Σ nidi number average diameter: Dm =-Σ ni D« / Dn The ratio represents the distribution of particle size, sometimes Also known as "particle size distribution width." The measurement method using the Optoniax image analyzer is by changing the magnification of the microscope 16 to 200 times, observe the support of the skull or (please read the precautions on the back before filling in this page). Installed--Line · Printed by the Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperative. ) A4 specifications (210x297 mm) _ ^ g〇5〇 ^ r · Λ 6 B6 Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention () A suspension of catalyst particles. The TV camera uses a transformation microscope Pick the image, and input the picked image into the computer. The computer analyzes the image line by line to measure the orientation or diameter of the particles, and then classifies them. The following example will illustrate the present invention: m 1 漢 备 柏 活 彳 H 本 ant 88: 10. 2 liters of the mixture contains 10 moles of di-butyl magnesium in n-hexane, 6.45 liters of n-hexane Alkane and the last 1 liter of diisoamyl ether, etc. In the first step, at room temperature and 25 death, under nitrogen, the ore was added to a 30 liter stainless steel reactor with agitation of 600 rpm. Ito and a shell. In the second step, the speed of the stirring system was maintained at 600 revolutions per minute and the temperature in the reactor was maintained at 25 ° C. 2.4 liters of tert-butyl gas was added to the mixture and maintained at a fixed speed for 12 hours. After the time expired, the mixture was maintained at 2'51 ° for 3 hours. The resulting precipitate was rinsed with 15-liter n-hexane. Repeat the flushing sediment 6 times. The solid product obtained is a pre-activated support (Α) which is planted on magnesium oxychloride. The solid product contains 12% of diisoamyl ether relative to magnesium nitride. When examined by explicit microscopy, the pre-activation support compound (A) exists in the form of spherical particles with a mass average diameter of 21 mm and a fairly narrow particle size distribution, for example, the Dm / 〇 „size ratio of the particles is equal to 1.4. The specific area of the pre-activated support (A) is approximately 45i2 / g (BET). The structure of the magnesium oxide in the pre-activated support bet is indefinite. 12 I Chi 11 The pre-activated support prepared in Example 1 ( A) The suspension contains 4 mol of vaporized magnesium in n-hexane. The pre-activated support (A) is added to a 30-liter stainless-pin reactor under nitrogen. This reactor is equipped with Read the precautions on the back first and then fill out this page) < Binding · The size of the paper used in the Chinese National Standard (CNS) A 4 specifications (210x297 mm) _ 19 _ 2〇5〇4 · A 6 Β6 Central Ministry of Economic Affairs Printed by Beigong Consumer Cooperative of the Bureau of Standards 5. Description of the invention () 35 rpm agitating system. This suspension is kept under constant stirring at room temperature 25 υ, adding 18 liters of n-hexane, slow at a rate of more than 30 minutes Slowly add 0.365 liters of n-butanol, at 251C, keep stirring for 1 hour to get the activated support. Hold the suspension. After the time is up, stop the stirring to precipitate the activated support, remove the upper layer liquid, and resuspend the activated support in the 6-liter positive-health hospital with stirring. In the second step, .1 〇 One liter of n-hexane is added to the final suspension of the activated support, and the stirring is maintained at 251G. Then, 46 liters of ethylbenzene is slowly added at a rate of more than 30 minutes. The treated support skull suspension Hold and stir at 25Ό for 1 hour. After the time is up, stop stirring to precipitate the support skeleton and remove the upper layer liquid. The treated support is washed with 20 liters of n-hexane each time at 25 ° C. , Keep the suspension stirred for 15 minutes during each wash, then allow the treated support to settle for 20 minutes, remove the upper fluid, resuspend the support, and finally suspend the treated support in 6 liters of n-hexane. In the third step, 6 liters of titanium tetranitride was added to the final suspension of the treated support skeleton under stirring at 25t :. The obtained suspension was heated to 100 ° C and held stirring at this temperature 2 hours. End of time, saturated support suspension Stir and cool to 50Ό, and then stop stirring to precipitate the saturated support, remove the upper layer liquid, the saturated support is bet under 5QTC, each time with 20 liters of n-hexane continuous washing three times, then at 25 ^, each 20 liters of n-hexane was washed twice. Finally, the impregnated support (B) was resuspended in 6 liters of n-hexane at 25 TC. The spherical particles 1 contained 6¾ titanium atoms per magnesium atom. (Please read first (Notes on the back will be written on this page) Binding · Ordering _ Line-All paper sizes are used in a B home «quasi (CNS) A 4 specifications (210X297 male dragon) -20-2〇5〇β Λ6 Β6 Ministry of Economic Affairs Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards 5. Description of the invention () In the fourth tilting step, 9 liters of titanium tetrachloride are added to the final suspension of the impregnated support (B) under 25TC mixing, The obtained suspension was heated to 1QQO and kept entangled and stirred at this temperature for 2 hours. After the time is up, the obtained catalyst suspension is stirred and cooled to 50 ° C, and then the search and mixing are stopped to precipitate the catalyst, and the upper layer liquid is removed. The catalyst is continuously set with 20 liters of n-hexane each time at 50 Wash three times. At 25 ° C, wash with the 20-liter Zhengjiyuan four times in a row. The catalyst (C) is separated and stored in nitrogen. It contains 5.5% of titanium atoms per magnesite. It contains spheres with a mass average diameter of 21w; shaped particles with a particle size distribution D »/ Dn ratio of 1.4. (A) #TFR alkane concealed liquid Φ 馎 prepared for gathering together. In a cubic meter of stainless steel reactor, the device spins at 140 rpm every minute at 601D, keeping it under nitrogen pressure, adding 450 liters in series N-hexane, 2.05-ear tri-n-octyl aluminum, and the catalyst (C) containing 0.41 mol titanium prepared in Example 2 and liquid propylene (added at a steady flow rate of 18 kg / hour). The reaction was terminated after 4 hours and 20 minutes, and the reactor was vented. The obtained prepolymer was washed three times with 300 liters of n-hexane. The material in the reactor was transferred to a dryer, and n-hexane was removed by evaporation using hot krypton vapor. A dry prepolymer (D) is obtained, which is a non-viscous powder with the following properties:-Titanium content: 25 0 ρρπ-Aluminum / titanium ratio in prepolymer (D): 2-Titanium per millimolar The amount of prepolymer obtained: 190 grams (please read the precautions on the back before filling in this page) Binding · Order-Line. This paper size uses the Chinese B home sample standard (CNS) A 4 specifications (210X297 g *)- 21-20504 *? Λ6 B6 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention ()-Apparent density: 0.330 g / cm3-Average particle mass diameter: 110 iu. (In the sickle type is very cooked. 7. The preparation is performed in a fluidized bed reactor. It is 0.45 meters in diameter and 7 meters in height. A fluidization grid (fluidization grid) is installed in the lower part. ), And supports a vertical figure of the skull out of the chamber. The reactor device has an external gas recirculation conduit connecting the top of the top to the lower part of the reactor below the fluidization grid, and a ring compressor and heat conduction. Plants and equipment. The main components of the reaction gas mixture such as ethylene, 1-butene, hydrogen and ® are fed into the fluidized bed using a feed conduit, and more particularly can enter the recirculation conduit when it overflows. The fluidized bed should be fixed at 1.8 meters above the fluidized grid. This fluidized bed contains 70 kg of linear very low density polyethylene powder being formed. The reactor is heated to 60 and it is added at a rate of 0.25 kg / hour Prepolymer (D). The total pressure of this reaction gas mixture is 1.6 MPa and rises from the fluidized bed at an upward flow rate of 0.55 m / s. It contains 30% ethylene by volume and 11% bu Butene, 12% hydrogen and 47% nitrogen. Under these conditions, linear very low density polyethylene is prepared at a rate of 15 kg / hour, which is in the form of powder, has good fluidity, and has the following properties: a specific density: 0.900 — derived from 1-butene The weight of the unit is fluctuating: 17.5%-in 2 liters, 190t: the measured melt index MI2: 1 g / 10 min (please read the precautions on the back and fill in. Write this book) -install · order- Thread · This paper standard is commonly used in 8 National Standards (CNS) A 4 specifications (210x297 g *)-22-A 6 Β6 2〇5ΰ4? 5. Description of invention () Clock (Please read the precautions on the back before filling this page )-Apparent density: 0.390 g / cm3-Qin_ content: 4ρρ · One particle mass average diameter D «: 430 W -Dn / Dn ratio: 1.6 One fluidity: 20 seconds m 4 (A) Store TF R alkanto Propylene in the liquid selection refers to the preparation of gatherings: In a 1m3 stainless steel reactor, it is equipped with a rotating stirrer with 140 revolutions per minute, and at 60TC, maintaining nitrogen pressure, Burma added 450 liters of n-hexane , 1.09 moles of triethylaluminum, 0.545 moles of diethylaluminum cyanide, and the contact prepared in Example 2 Medium (C) (which contains 0.41 mol titanium) and liquid propylene (its addition rate is 18 kg / h). After 4 hours and 20 minutes, the addition of propylene was stopped and the reactor was vented. The resulting prepolymer was 300 liters The n-hexane continuous ore was washed three times, the material in the reactor was transferred to a dryer, and the n-hexane was removed by evaporation with hot nitrogen vapor. Under this condition, a non-viscous powdery prepolymer (E), which has the following Features: Printed by the Central Bureau of Standards of the Ministry of Economic Affairs Beigong Consumer Cooperatives: one titanium containing child: 26〇ppb a dry prepolymer (E) aluminum / titanium ratio: 1.2-available prepolymer per millimolar of titanium Amount: 185 grams One-eye density: 0.46 grams / cubic centimeter (R) Sickle-type cooking dense hemp polyene Xi Ye prepared: The operation in the fluidized bed reactor is the same as Example 3-B. This reactor uses the Chinese Standard (CNS) A4 specifications (210x297 mm) for this paper scale. 23-
2〇5〇4!V Λ6 B6 經濟部中央標準局貝工消費合作社印製 五、發明説明（） 的流化床固定在流化格子上高度1.8公尺的地方，此流化 床中有70公斤的線型低密度聚乙烯粉末正在形成。反應器 加熱到80它，以《.25公斤/小時的速率加入預聚合物（£) ，及以50毫升/小時的流速加入含每公升正己烷中有1〇〇 毫莫耳的三乙基鋁的溶液。 反應氣睹混合物的總壓為1.6MPa,以0.52公尺/秒的 向上流速在流化床中升起。混合物含體積百分率為30%之 乙烯，4.5¾之1-丁烯，12%的氫和53.5%的氮。 在這些條件下，線型低密度聚乙烯以20公斤/小時2 速率被製備.其為粉末狀的形式，具有很好的流動性，·& 具下列性質： 一比密度：0 . 9 2 一由1-丁烯衍生之單位的重量含量：7.5% 一 2公斤裝，在1901C下測得之融解指數MI2 : 0.6克/10 分鐘 —視密度：0.480克/立方公分 一鈦含量：3 PPB 一粒子質量平均直徑: 480 w 一 Dm/ D„比率：1.8 例5 (A)#TF R烷鶼浮液Φ靱備丙烯指聚合物 此操作與例4-A的操作相同。 (R)锶型飪密庠聚Z烯的剪備 此操作在流化床反應器中進行，除了以4-甲基-卜戊 本紙張尺度逍用中B Η家標準(CNS)肀4規格(210X2974*) (請先閱讀背面之注意事項再填寫本黃) 装. 订 -線· Λ6 B6 經濟部中央標準局貝工消费合作社印製 五、發明説明（） 烯取代-1 丁烯進料以外，其他操作方法均與例3-8相同。 此方法器之流化床固定於流化格子上高度1.8公尺之處， 反應器中含7 0公斤線型低密度聚乙烯正在形成中。反應器 加熱到8 01 ,次〇 . 2¾公斤/小時的速率加入預聚合物（E) 和以50毫升/小時的流率加入含有毎升正己烷中有100毫 莫耳三乙基鋁的溶液。 反應氣賭混合物總歷為1.6MPa,以0.5公尺/秒的向 上流動速度由流化床中升起，其含有體積百分率為30%之 乙烯、3%之4-甲基-1-戊烯，12%之氫氣，55%之氮氣 Ο 在這些條件下，線型低密度聚乙烯以15公斤/小時之 速率被製備.其為具有很好流動性的粉末，且具有下列特 性： 一比密度：0.919 一由4-甲基-1-戊烯衍生之單位的重量含量：9.5% -在2公斤裝，1901C下測得之融解指數MI2: 1公克/10 分鐘 一視密度：0.45 0克/立方公分 一粒子質蛋平均直徑D» : 480 χζ 一 D»/ Dn比率：1.8 (請先閱讀背面之注意事項再填寫本頁) 裝. . 線- 本紙張尺度逍用中Β B家橾毕(CNS)甲4規格(210x297公*) 252〇5〇4! V Λ6 B6 Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. The description of the invention () The fluidized bed is fixed on a fluidized grid at a height of 1.8 meters. There are 70 in this fluidized bed Kg of linear low density polyethylene powder is being formed. The reactor was heated to 80 ° C, the prepolymer (£) was added at a rate of .25 kg / hour, and triethyl ester containing 100 millimoles per liter of n-hexane was added at a flow rate of 50 ml / hour. Aluminum solution. The total pressure of the reaction gas mixture is 1.6 MPa, and it rises in the fluidized bed at an upward flow rate of 0.52 m / s. The mixture contains 30% by volume of ethylene, 4.5¾ of 1-butene, 12% of hydrogen and 53.5% of nitrogen. Under these conditions, linear low-density polyethylene is prepared at a rate of 20 kg / h 2. It is in powder form and has good fluidity. · &Amp; has the following properties: 1. Specific density: 0.9 2 1. Weight content of units derived from 1-butene: 7.5%-2 kg, melt index MI2 measured at 1901C: 0.6 g / 10 min-apparent density: 0.480 g / cm3-titanium content: 3 PPB- Particle mass average diameter: 480 w-Dm / D "Ratio: 1.8 Example 5 (A) #TF R Alkanol Floating Liquid ΦTai Propylene Refers to Polymer This operation is the same as that of Example 4-A. (R) Strontium type The preparation of dense polyolefins is carried out in a fluidized bed reactor, except for the 4-methyl-bupentan paper scale, which is used in the Chinese Standard (CNS) 4 specifications (210X2974 *) ( Please read the precautions on the back before filling in this yellow) Packing. Order-line · Λ6 B6 Printed by Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Description of the invention () Other than ene-1 butene feed, other methods of operation Both are the same as in Examples 3-8. The fluidized bed of this method is fixed at a height of 1.8 meters on the fluidized grid, and the reactor contains 70 meters The linear low-density polyethylene is being formed. The reactor is heated to 801, and the prepolymer (E) is added at a rate of 0.22 kg / hour and at a flow rate of 50 ml / hour. A solution of 100 millimoles of triethylaluminum. The reaction gas mixture has a total history of 1.6 MPa and rises from the fluidized bed at an upward flow rate of 0.5 m / s. It contains ethylene, 3% by volume, and 3% by volume. % 4-methyl-1-pentene, 12% hydrogen, 55% nitrogen Ο Under these conditions, linear low density polyethylene is prepared at a rate of 15 kg / h. It is very fluid The powder has the following characteristics: a specific density: 0.919 a weight content of the unit derived from 4-methyl-1-pentene: 9.5%-a melting index MI2 measured at 1901C in a 2 kg package: 1 g / The apparent density in 10 minutes: 0.45 0 g / cm3 The average diameter of a grain of egg D »: 480 χζ one D» / Dn ratio: 1.8 (please read the precautions on the back before filling this page) Pack.. Thread-this Paper-scale Happy Use Β B Family Standard (CNS) Grade 4 (210x297 g *) 25